WO2015186753A1 - Plaque de verre trempée chimiquement dotée d'un film fonctionnel, son procédé de production et article - Google Patents

Plaque de verre trempée chimiquement dotée d'un film fonctionnel, son procédé de production et article Download PDF

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Publication number
WO2015186753A1
WO2015186753A1 PCT/JP2015/066087 JP2015066087W WO2015186753A1 WO 2015186753 A1 WO2015186753 A1 WO 2015186753A1 JP 2015066087 W JP2015066087 W JP 2015066087W WO 2015186753 A1 WO2015186753 A1 WO 2015186753A1
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Prior art keywords
glass plate
functional film
chemically strengthened
film
strengthened glass
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PCT/JP2015/066087
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English (en)
Japanese (ja)
Inventor
義美 大谷
敏 本谷
一倫 森
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旭硝子株式会社
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Publication of WO2015186753A1 publication Critical patent/WO2015186753A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
    • C03C17/23—Oxides
    • C03C17/25—Oxides by deposition from the liquid phase
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C21/00—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
    • C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal

Definitions

  • the present invention relates to a chemically strengthened glass plate with a functional film, a method for producing a chemically strengthened glass plate with a functional film, a chemically strengthened glass plate with a functional film obtained by the production method, and an article comprising the chemically strengthened glass plate with the functional film. .
  • a functional film such as an antiglare film and a low reflection film have been formed on the surface of a glass plate.
  • a coating solution containing a silica precursor such as alkoxysilane is applied on a glass plate and dried or baked.
  • This method has a simple process, and the performance of the functional film can be controlled by the composition of the coating solution and the coating method. For example, when a material having a low refractive index is blended in the coating solution, a functional film having low reflectivity is formed. Moreover, when a coating liquid is applied so that irregularities are formed on the surface, a functional film having an antiglare property is formed.
  • the glass plate is strengthened by a chemical strengthening method.
  • a glass plate is immersed in a molten salt at a temperature lower than the strain point temperature of the glass, and ions (for example, sodium ions) on the surface of the glass plate are exchanged for ions having a larger ion radius (for example, potassium ions). To do.
  • ions for example, sodium ions
  • ions having a larger ion radius for example, potassium ions
  • ion exchange through the low-reflection film can be performed by using a coating solution containing a specific silicon compound, a hollow silica sol, and a metal chelate compound in a specific weight ratio for forming the low-reflection film. It is possible to perform chemical strengthening treatment effectively.
  • Patent Document 1 is not suitable for forming a functional film other than the low reflection film because the composition of the coating solution is limited. Further, the material for forming the functional film is expensive because it needs to contain a relatively expensive hollow silica sol at a predetermined ratio. Furthermore, the chemical strengthening effect of the glass plate is not sufficient.
  • the present invention has been made in view of the above circumstances, and a method for producing a chemically tempered glass plate with a functional film that can satisfactorily chemically strengthen the glass plate after forming the functional film, and a chemical tempering with a functional film obtained by the production method. It aims at providing the articles
  • the present invention has the following aspects.
  • a chemically strengthened glass plate provided with a functional film containing a silica-based matrix on at least one surface, wherein the portion having the functional film containing the silica-based matrix is before and after the abrasion resistance test.
  • a chemically strengthened glass plate with a functional film having a wear resistance of 20 or less as a difference in 60 ° specular gloss in each.
  • the portion having the functional film has an abrasion resistance of 10 or less as a difference in 60 ° specular gloss before and after the abrasion resistance test, according to [1] or [2]
  • the chemically strengthened glass plate with a functional film as described.
  • the chemically strengthened glass plate is expressed in terms of a molar percentage based on oxide, and includes SiO 2 of 56 to 75%, Al 2 O 3 of 1 to 20%, Na 2 O of 8 to 22%, and K 2 O of The chemically strengthened glass with a functional film according to any one of [1] to [4], containing 0 to 10%, MgO 0 to 14%, ZrO 2 0 to 5%, and CaO 0 to 10%. Board.
  • the chemically strengthened glass plate with a functional film according to any one of [1] to [6], wherein the functional film further includes solid inorganic particles.
  • Coating solution at least one silica precursor selected from the group consisting of a silane compound having a hydrolyzable group bonded to a silicon atom and a hydrolysis condensate thereof, and a liquid medium, and the content of the silica precursor However, it is 15 mass% or more with respect to the oxide conversion solid content in the said coating liquid.
  • a method for producing a chemically strengthened glass plate with a functional film in which a functional film is formed on a glass plate, and the glass plate is subjected to a chemical strengthening treatment A functional film is formed from the following coating solution at a temperature of 450 ° C. or lower, and then a glass plate that has not been heat-treated at a temperature higher than 450 ° C.
  • a method for producing a chemically strengthened glass plate with a functional film which is characterized. Coating solution: at least one silica precursor selected from the group consisting of a silane compound having a hydrolyzable group bonded to a silicon atom and a hydrolysis condensate thereof, and a liquid medium, and the content of the silica precursor However, it is 15 mass% or more with respect to the oxide conversion solid content in the said coating liquid.
  • the coating liquid further contains solid inorganic particles, and the content of the solid inorganic particles is 10 to 85% by mass with respect to the oxide-converted solid content in the coating liquid.
  • Thru or the manufacturing method of the chemically strengthened glass plate with a functional film as described in any one of [10].
  • a chemically strengthened glass plate with a functional film obtained by the method for producing a chemically strengthened glass plate with a functional film according to any one of [8] to [11].
  • An article comprising the chemically strengthened glass plate with a functional film according to any one of [1] to [7] and [12].
  • the manufacturing method of the chemically strengthened glass plate with a functional film which can chemically strengthen a glass plate, the chemically strengthened glass plate with a functional film obtained by this manufacturing method, and with this functional film An article comprising a chemically strengthened glass plate can be provided.
  • the functional film is cured, and physical deterioration due to contact with an object is suppressed.
  • the “chemically tempered glass plate” is a glass plate tempered (chemically strengthened) by a chemical strengthening method.
  • the chemical strengthening method is one of the methods for forming a compressive stress layer on the surface of the glass plate.
  • the glass plate is immersed in a molten salt at a temperature equal to or lower than the strain point temperature of the glass, and ions on the surface of the glass plate (for example, sodium).
  • ions on the surface of the glass plate for example, sodium
  • This is a method of exchanging ions) for ions having a larger ion radius (for example, potassium ions).
  • compressive stress arises in a glass plate surface layer.
  • the strain point of glass is lower than the softening point.
  • the “compressive stress layer” is a layer (chemical strengthening layer) having a desired surface compressive stress.
  • the surface compressive stress of the chemically strengthened glass plate and the thickness of the compressive stress layer are measured by a surface stress meter (for example, FSM-6000LE manufactured by Orihara Seisakusho).
  • “Silica precursor” means a substance capable of forming a matrix mainly composed of silica.
  • “Containing silica as a main component” means containing 90 mass% or more of SiO 2 .
  • the “hydrolyzable group bonded to a silicon atom” means a group that can be converted into an OH group bonded to a silicon atom by hydrolysis.
  • Oxide conversion solid content means the sum total of the oxide conversion (metal oxide conversion) content of the component containing a metal element among the components contained in a coating liquid. Content shown as a ratio with respect to oxide conversion solid content is content of oxide conversion.
  • the content of the silica precursor is an amount equivalent to SiO 2 . That is, the content when all Si contained in the silica precursor is converted to SiO 2 .
  • FIG. 1 is a cross-sectional view schematically showing an example of a chemically strengthened glass plate with a functional film of the present invention.
  • the chemically strengthened glass plate 1 with a functional film in this example includes a functional film 5 and a chemically strengthened glass plate 3 having the functional film 5 on the surface.
  • a glass plate on which the functional film 5 is formed (a glass plate before chemical strengthening: an unstrengthened glass plate) may be referred to as a glass plate 3.
  • the functional film 5 may be a single layer film or a multilayer film.
  • the thickness of the chemically strengthened glass plate 3 is preferably less than 2 mm, more preferably 0.33 mm to 1.1 mm, and particularly preferably 0.7 mm to 1.1 mm.
  • a glass plate having a thickness of less than 2 mm is difficult to strengthen by the air-cooling strengthening method. Therefore, the usefulness of this invention is high when the thickness of the glass plate to strengthen is less than 2 mm.
  • the mass of the chemically strengthened glass plate 1 with a functional film per unit area becomes light, and an article provided with the chemically strengthened glass plate 1 with a functional film can be reduced in weight.
  • the thickness of the chemically strengthened glass plate 3 is 0.33 mm or more, even when the chemically strengthened glass plate 1 with a functional film is large (for example, the long side is 300 mm or more), the deflection is small and easy to handle.
  • the chemically strengthened glass plate 3 preferably has a surface compressive stress of 400 MPa or more and a compressive stress layer thickness of 5 ⁇ m or more. If the surface compressive stress is 400 MPa or more and the thickness of the compressive stress layer is 5 ⁇ m or more, the chemically strengthened glass plate 3 is excellent in durability against physical impacts such as scratches.
  • the surface compressive stress of the chemically strengthened glass plate 3 is more preferably 500 MPa or more, and further preferably 600 MPa or more, depending on the application. Typically, the surface compressive stress is 800 MPa or less.
  • the thickness of the compressive stress layer is more preferably 10 ⁇ m or more, even more preferably 20 ⁇ m or more, and even more preferably more than 25 ⁇ m. Further, typically, the thickness of the compressive stress layer is 70 ⁇ m or less.
  • the chemically strengthened glass plate 3 includes a functional film 5 on at least one surface.
  • the functional film 5 is provided on at least a part of the glass plate 3.
  • the functional film 5 may be provided on a part of one surface of the glass plate 3 or may be provided so as to cover the entire surface of the one surface.
  • the functional film 5 is applied with a coating solution containing at least one silica precursor selected from the group consisting of a silane compound having a hydrolyzable group bonded to a silicon atom and a hydrolysis condensate thereof, and a liquid medium, It is formed by drying.
  • the functional film 5 includes a matrix mainly composed of silica (hereinafter also referred to as a silica-based matrix) formed from a silica precursor.
  • a silica-based matrix is one in which 50% or more of silica is contained in the matrix.
  • the silica-based matrix may contain components other than silica.
  • the components include Li, B, C, N, F, Na, Mg, Al, P, S, K, Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, and Sr. , Y, Zr, Nb, Ru, Pd, Ag, In, Sn, Hf, Ta, W, Pt, Au, Bi and compounds such as one or more ions and / or oxides selected from the group of lanthanoid elements Is mentioned.
  • the functional film 5 may be composed of only a silica-based matrix, or may further include components other than the silica-based matrix. For example, particles dispersed in a silica-based matrix may be included. The type of particles and the like will be described in detail in the section of the coating liquid for producing the functional film.
  • the functional film 5 is not particularly limited as long as it can be formed from a coating solution containing the silica precursor and a liquid medium.
  • an antiglare film, a low reflection film, a glass anti-glare film, an alkali barrier film examples thereof include a flaw prevention film and an antifouling film.
  • an antiglare film or a low reflection film is preferable because it is highly necessary in many applications in which chemically strengthened glass is used.
  • the antiglare film is a film having an antiglare property.
  • the antiglare film may be an antiglare film having low reflectivity (that is, a low reflectivity antiglare film).
  • the low reflection film is a film having low reflectivity (that is, antireflection property).
  • the 60 ° specular gloss on the surface of the functional film 5 is preferably 80% or less, more preferably 70% or less, and even more preferably 60% or less. If the 60 ° specular gloss on the surface of the functional film 5 is 80% or less, the antiglare effect is sufficiently exhibited.
  • the arithmetic average roughness Ra of the surface of the functional film 5 is preferably 0.04 to 1.00 ⁇ m, more preferably 0.06 to 1.00 ⁇ m, and more preferably 0.1 to 0 More preferably, it is 8 ⁇ m. If the arithmetic average roughness Ra of the surface of the functional film 5 is not less than the lower limit of the above range, the antiglare effect is sufficiently exhibited. If the arithmetic average roughness Ra of the surface of the functional film 5 is less than or equal to the upper limit of the above range, when the chemically strengthened glass plate 1 with the functional film is provided on the viewing side of the image display device body as a protective plate or various filters, A decrease in image contrast is sufficiently suppressed.
  • the refractive index of the functional film 5 is preferably 1.23 to 1.47, and more preferably 1.25 to 1.40.
  • the refractive index of the functional film 5 is not more than the upper limit of the above range, reflection on the surface of the functional film 5 is suppressed, and the light transmittance is improved as compared with the case of the chemically strengthened glass plate 3 alone.
  • the refractive index of the functional film 5 is equal to or higher than the lower limit of the above range, the functional film 5 is dense and excellent in mechanical strength such as wear resistance of the functional film 5 and adhesion to the chemically strengthened glass plate 3.
  • the chemically strengthened glass plate 1 with a functional film is provided as a cover crow on the light incident side of the solar cell, the power generation efficiency of the solar cell is good.
  • the thickness of the functional film 5 is preferably 30 to 300 nm, and more preferably 40 to 200 nm. If the film thickness of the functional film 5 is 30 nm or more, light interference occurs and low reflection performance is exhibited. If the film thickness of the functional film 5 is 300 nm or less, the film can be formed without generating cracks. The film thickness of the functional film 5 is measured by the reflectance measured by a spectrophotometer.
  • the reflectance of the functional film 5 is the lowest value (so-called bottom reflectance) in the wavelength range of 300 to 1200 nm, preferably 2.6% or less, and 1.0% The following is more preferable.
  • the portion provided with the functional film 5 (hereinafter also referred to as a functional film surface) has a 60 ° specular gloss difference before and after the abrasion resistance test of 60 or less, more preferably 55 or less, and even more preferably 50 or less.
  • the abrasion resistance test can be performed with an abrasion resistance tester (hereinafter also referred to as a rubbing tester) in which a friction element such as an eraser, steel wool, felt, or the like is attached to the tip, and reciprocation is possible under a constant load.
  • a friction element such as an eraser, steel wool, felt, or the like
  • the 60 ° specular glossiness on the functional film surface side is measured based on JIS Z8741 after being prevented from the influence of reflection from the surface opposite to the functional film surface of the chemically strengthened glass plate 3.
  • the specular reflection component from the surface with respect to the incident light from the predetermined incident angle increases. Therefore, the smaller the change in the 60 ° specular gloss, the better the wear resistance.
  • the functional film 5 has a 60 ° specular gloss difference of 20 or less before and after the abrasion resistance test because physical deterioration due to contact with an object is suppressed and a functional film excellent in long-term durability can be obtained. It is preferable that it has abrasion resistance, More preferably, it is 15 or less, More preferably, it is 10 or less. When there is substantially no change in 60 ° specular gloss, that is, when the difference in 60 ° specular gloss before and after the abrasion resistance test is 0, the abrasion resistance is most preferable.
  • the chemically strengthened glass plate 1 with a functional film is, for example, A step of applying the following coating solution onto a glass plate and drying to form the functional film 5 (hereinafter also referred to as “functional film forming step”);
  • the glass plate on which the functional film 5 is formed can be chemically strengthened to obtain a chemically strengthened glass plate 1 with a functional film (hereinafter also referred to as “chemical strengthening step”).
  • chemical strengthening step You may perform the process of giving a well-known post-process with respect to the chemically strengthened glass plate 1 with a functional film after a chemical strengthening process as needed.
  • the functional film is a chemically strengthened glass plate with a functional film provided in a part of the chemically strengthened glass plate 3, for example, the portion of the surface of the chemically strengthened glass plate 3 that does not form the functional film is masked.
  • a film may be formed.
  • the coating liquid contains at least one silica precursor selected from the group consisting of a silane compound having a hydrolyzable group bonded to a silicon atom and a hydrolysis condensate thereof, and a liquid medium.
  • the coating solution may further contain particles, a terpene compound, an additive, and the like as necessary.
  • Silica precursor As the silica precursor, a silane compound having a hydrocarbon group bonded to a silicon atom and a hydrolyzable group (hereinafter also referred to as A1), a hydrolysis condensate thereof, and alkoxysilane (however, a silane compound (A1) is excluded). And its hydrolyzed condensate (sol-gel silica).
  • the hydrocarbon group bonded to the silicon atom may be a monovalent hydrocarbon group bonded to one silicon atom, or a divalent hydrocarbon group bonded to two silicon atoms.
  • the monovalent hydrocarbon group include an alkyl group, an alkenyl group, and an aryl group.
  • the divalent hydrocarbon group include an alkylene group, an alkenylene group, and an arylene group.
  • the hydrocarbon group is selected from the group consisting of —O—, —S—, —CO— and —NR′— (wherein R ′ is a hydrogen atom or a monovalent hydrocarbon group) between carbon atoms.
  • R ′ is a hydrogen atom or a monovalent hydrocarbon group
  • Examples of the hydrolyzable group bonded to the silicon atom include an alkoxy group, an acyloxy group, a ketoxime group, an alkenyloxy group, an amino group, an aminoxy group, an amide group, an isocyanate group, and a halogen atom.
  • an alkoxy group, an isocyanate group, and a halogen atom are preferable from the viewpoint of the balance between the stability of the silane compound (A1) and the ease of hydrolysis.
  • As the alkoxy group an alkoxy group having 1 to 3 carbon atoms is preferable, and a methoxy group or an ethoxy group is more preferable.
  • the hydrolyzable groups may be the same group or different groups, and it is easy to obtain that they are the same group. This is preferable.
  • silane compound (A1) examples include a compound represented by the formula (I) described later, an alkoxysilane having an alkyl group (methyltrimethoxysilane, ethyltriethoxysilane, etc.), an alkoxysilane having a vinyl group (vinyltrimethoxysilane).
  • alkoxysilanes having an epoxy group (2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane) And 3-glycidoxypropyltriethoxysilane) and alkoxysilanes having an acryloyloxy group (such as 3-acryloyloxypropyltrimethoxysilane).
  • silane compound (A1) a compound represented by the following formula (I) is preferable from the viewpoint that even if the film thickness is large, the functional film is not easily cracked or peeled off.
  • Q is a divalent hydrocarbon group (-O—, —S—, —CO— and —NR′— (where R ′ is a hydrogen atom or a monovalent hydrocarbon) And a group obtained by combining one or two or more selected from the group consisting of: What was mentioned above is mentioned as a bivalent hydrocarbon.
  • Q is preferably an alkylene group having 2 to 8 carbon atoms, and is preferably an alkylene group having 2 to 6 carbon atoms from the viewpoint that it is easily available, and even if the film thickness is large, the functional film is less likely to crack or peel off. Further preferred.
  • L is a hydrolyzable group.
  • the hydrolyzable group include those described above, and preferred embodiments are also the same.
  • R is a hydrogen atom or a monovalent hydrocarbon group. Examples of the monovalent hydrocarbon include those described above.
  • p is an integer of 1 to 3. p is preferably 2 or 3, particularly preferably 3, from the viewpoint that the reaction rate does not become too slow.
  • alkoxysilane examples include tetraalkoxysilane (tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, etc.), alkoxysilane having a perfluoropolyether group ( Perfluoropolyether triethoxysilane and the like), alkoxysilanes having a perfluoroalkyl group (perfluoroethyltriethoxysilane and the like), and the like.
  • tetraalkoxysilane tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, etc.
  • alkoxysilane having a perfluoropolyether group Perfluoropolyether triethoxysilane and the like
  • alkoxysilanes having a perfluoroalkyl group
  • Hydrolysis and condensation of the silane compound (A1) and alkoxysilane (excluding the silane compound (A1)) can be carried out by a known method.
  • the reaction is carried out using 4 times or more moles of water of tetraalkoxysilane and acid or alkali as a catalyst.
  • the acid include inorganic acids (HNO 3 , H 2 SO 4 , HCl, etc.) and organic acids (formic acid, oxalic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, etc.).
  • the alkali include ammonia, sodium hydroxide, potassium hydroxide and the like.
  • an acid is preferable from the viewpoint of long-term storage stability of the hydrolysis condensate of the silane compound (A).
  • a silica precursor 1 type may be used independently and 2 or more types may be used in combination. It is preferable that a silica precursor contains either one or both of a silane compound (A1) and its hydrolysis condensate from a viewpoint of preventing the crack of a functional film, and film
  • the silica precursor preferably contains either one or both of tetraalkoxysilane and its hydrolysis condensate from the viewpoint of the wear resistance strength of the functional film. It is particularly preferable that the silica precursor contains one or both of the silane compound (A1) and the hydrolysis condensate thereof, and one or both of the tetraalkoxysilane and the hydrolysis condensate thereof.
  • the liquid medium dissolves or disperses the silica precursor, and is preferably a solvent that dissolves the silica precursor.
  • the liquid medium may also have a function as a dispersion medium for dispersing the particles.
  • the liquid medium include water, alcohols, ketones, ethers, cellosolves, esters, glycol ethers, nitrogen-containing compounds, and sulfur-containing compounds.
  • Examples of alcohols include methanol, ethanol, isopropanol, 1-butanol, 2-butanol, isobutanol, diacetone alcohol, and the like.
  • Examples of ketones include acetone, methyl ethyl ketone, and methyl isobutyl ketone.
  • Examples of ethers include tetrahydrofuran and 1,4-dioxane.
  • Examples of cellosolves include methyl cellosolve and ethyl cellosolve.
  • Examples of esters include methyl acetate and ethyl acetate.
  • Examples of glycol ethers include ethylene glycol monoalkyl ether.
  • nitrogen-containing compound examples include N, N-dimethylacetamide, N, N-dimethylformamide, N-methylpyrrolidone and the like.
  • sulfur-containing compound examples include dimethyl sulfoxide.
  • a liquid medium may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the liquid medium contains at least water unless the liquid medium is replaced after hydrolysis.
  • the liquid medium may be water alone or a mixed liquid of water and another liquid.
  • other liquids include alcohols, ketones, ethers, cellosolves, esters, glycol ethers, nitrogen-containing compounds, and sulfur-containing compounds.
  • alcohols are preferable, and methanol, ethanol, isopropyl alcohol, 1-butanol, 2-butanol, and isobutanol are particularly preferable.
  • the liquid medium may contain acid or alkali.
  • the acid or alkali may be added as a catalyst for hydrolysis and condensation of raw materials (alkoxysilane, etc.) during the preparation of the silica precursor solution, and is added after the preparation of the silica precursor solution. It may be a thing.
  • the coating liquid contains particles
  • the characteristics of the functional film 5 (refractive index, transmittance, reflectance, color tone, conductivity, wettability, physical durability, chemical durability, etc.) depend on the type and amount of particles. Can be adjusted. Examples of the particles include inorganic particles and organic particles.
  • Examples of the material for the inorganic particles include metal oxides, metals, alloys, and inorganic pigments.
  • the metal oxide include Al 2 O 3 , SiO 2 , SnO 2 , TiO 2 , ZrO 2 , ZnO, CeO 2 , Sb-containing SnO X (ATO), Sn-containing In 2 O 3 (ITO), RuO 2 and the like.
  • the metal include Ag and Ru.
  • Examples of the alloy include AgPd and RuAu.
  • Examples of inorganic pigments include titanium black and carbon black.
  • Examples of the organic particle material include organic pigments and resins.
  • Examples of the resin include polystyrene and melanin resin.
  • the particle shape examples include a spherical shape, an elliptical shape, a needle shape, a plate shape, a rod shape, a cone shape, a columnar shape, a cube shape, a rectangular shape, a diamond shape, a star shape, and an indefinite shape.
  • the particles may be solid particles, hollow particles, or perforated particles such as porous particles. “Solid” indicates that there is no cavity inside. “Hollow” indicates that there is a cavity inside.
  • the solid inorganic particles may exist in a state where each particle is independent, each particle may be linked in a chain shape, or each particle may be aggregated. The particles may be used alone or in combination of two or more.
  • solid inorganic particles are preferable from the viewpoint of cost and availability, and solid metal oxide particles are more preferable from the viewpoint of chemical durability. Solid inorganic particles and other particles may be used in combination.
  • solid silica particles may be included as solid inorganic particles.
  • the solid silica particles chain solid silica particles are preferable.
  • the chain solid silica particles are solid silica particles having a chain shape.
  • the shape of the chain solid silica particles can be confirmed by an electron microscope.
  • the chain solid silica particles can be easily obtained as a commercial product. Moreover, you may use what was manufactured by the well-known manufacturing method. Examples of commercially available products include Snowtex ST-OUP manufactured by Nissan Chemical Industries, Ltd.
  • the average aggregate particle diameter of the particles is preferably 5 to 300 nm, more preferably 5 to 200 nm. If the average agglomerated particle diameter of the particles is equal to or greater than the lower limit value of the above range, the effect of blending the particles is easily exhibited. If the average aggregate particle diameter is equal to or smaller than the upper limit value, the functional film 5 is excellent in mechanical properties such as wear resistance.
  • the average aggregate particle diameter of the particles is measured on a volume basis by a laser diffraction type particle size distribution measuring apparatus.
  • the terpene compound is preferably used when the coating solution contains particles.
  • the terpene means a hydrocarbon having a composition of (C 5 H 8 ) n (where n is an integer of 1 or more) having isoprene (C 5 H 8 ) as a structural unit.
  • the terpene compound means terpenes having a functional group derived from terpene. Terpene compounds also include those with different degrees of unsaturation.
  • terpene compounds function as a liquid medium
  • those having “a hydrocarbon having a composition of (C 5 H 8 ) n having isoprene as a structural unit” fall under the category of terpene derivatives. Shall not apply.
  • terpene compound terpene derivatives described in International Publication No. 2010/018852 can be used.
  • additive various known additives can be used.
  • a surfactant for improving leveling properties a metal compound for improving durability of the functional film 5, an ultraviolet absorber, an infrared reflector, an infrared ray Absorbers, antireflection agents and the like can be mentioned.
  • the surfactant include silicone oil and acrylic.
  • a zirconium chelate compound, a titanium chelate compound, an aluminum chelate compound and the like are preferable.
  • zirconium chelate compound include zirconium tetraacetylacetonate and zirconium tributoxy systemate.
  • the content of the silica precursor in the coating solution (in terms of SiO 2 ) is 15% by mass or more, more preferably 20% by mass or more, and more preferably 25% by mass or more based on the oxide-converted solid content in the coating solution. preferable. Adhesive strength sufficient between the chemically strengthened glass plate 3 and the functional film 5 is obtained when the content of the silica precursor (in terms of SiO 2 ) is 15% by mass or more with respect to the oxide-converted solid content.
  • the upper limit of the silica precursor content (SiO 2 equivalent) relative to the oxide equivalent solid content is not particularly limited, and may be 100% by mass. Content of a silica precursor can be suitably set according to content of the other component mix
  • the content of the liquid medium in the coating solution is an amount corresponding to the solid content concentration of the coating solution.
  • the solid content concentration of the coating solution is preferably 1 to 6% by mass and more preferably 2 to 5% by mass in the total amount (100% by mass) of the coating solution. If the solid content concentration is not less than the lower limit of the above range, the amount of the coating solution used for forming the functional film 5 can be reduced. If solid content concentration is below the upper limit of the said range, the uniformity of the film thickness of the functional film 5 will improve.
  • the solid content concentration of the coating solution is the total content of all components other than the liquid medium in the coating solution. However, content of the component containing a metal element is oxide conversion.
  • the content of the solid inorganic particles in the coating liquid is 10 to 85 mass with respect to the oxide-based solid content (100 mass%) in the coating liquid. %, More preferably 20 to 80% by mass, particularly preferably 30 to 75% by mass. If the content of the solid inorganic particles is not less than the lower limit of the above range, the blending effect of the solid inorganic particles can be sufficiently obtained. For example, in the case of solid silica particles, the refractive index of the functional film 5 is lowered, and a sufficient transmittance improvement effect is obtained. If the content of the solid inorganic particles is not more than the upper limit of the above range, the functional film 5 is excellent in mechanical strength such as wear resistance.
  • the coating liquid may or may not contain hollow silica particles as particles, but the content of the hollow silica particles in the coating liquid (in terms of SiO 2 ) is based on the oxide-converted solid content in the coating liquid. Less than 10% by mass. Preferably it is less than 7 mass%, More preferably, it is less than 5 mass%. If the content of the hollow silica particles is less than 10% by mass with respect to the oxide-converted solid content, unreinforced glass through the functional film 5 in the chemical strengthening step after forming the functional film on the unreinforced glass plate surface.
  • the plate can be sufficiently chemically strengthened, and the chemically strengthened glass plate 1 with a functional film can be produced at low cost.
  • the content (in terms of SiO 2 ) of the hollow silica particles in the coating solution is 0% by mass or more and less than 10% by mass, preferably 0% by mass or more and 7% by mass with respect to the oxide-converted solid content in the coating solution. %, More preferably 0% by mass or more and less than 5% by mass.
  • the coating liquid can be prepared, for example, by preparing a solution in which a silane precursor is dissolved in a liquid medium, and mixing an additional liquid medium, a dispersion of particles, a terpene compound, and other optional components as necessary.
  • the glass plate that forms a functional film and is chemically strengthened (hereinafter referred to as “unstrengthened glass plate”) is not particularly limited as long as it has a composition that can be chemically strengthened, and has various compositions. be able to.
  • soda lime glass and aluminosilicate glass can be suitably used.
  • aluminosilicate glass is preferable.
  • SiO 2 is 56 to 75%
  • Al 2 O 3 is 1 to 20%
  • Na 2 O is 8 to 22%
  • K 2 O is 0 to 0 in terms of mole percentage based on oxide.
  • a glass plate that is easily chemically strengthened is expressed in terms of a molar percentage based on oxide as a glass composition, SiO 2 is 60 to 75%, Al 2 O 3 is 2 to 25%, Na 2 O is 10 to 20%, K It is preferable to contain 0 to 7% 2 O, 0 to 10% MgO, and 0 to 15% CaO.
  • a glass plate that is easily chemically strengthened is expressed in terms of a molar percentage based on oxide as a glass composition, SiO 2 is 50 to 74%, Al 2 O 3 is 2 to 8%, Na 2 O is 8 to 18%, K 2 O 0 ⁇ 8% MgO 2 to 15% of ZrO 2 0 ⁇ 4% of CaO 0 ⁇ 10% of SrO 0-3%, it is preferable that the BaO containing 0-3%.
  • a glass plate that is easily chemically strengthened is expressed in terms of a molar percentage based on oxide as a glass composition, SiO 2 is 50 to 74%, Al 2 O 3 is 8 to 25%, Na 2 O is 8 to 18%, K 2 O 0 ⁇ 8% MgO 2 to 15% of ZrO 2 0 ⁇ 4% of CaO 0 ⁇ 10% of SrO 0-3%, it is preferable that the BaO containing 0-3%.
  • “containing 0 to 10% of K 2 O” means not necessarily essential but may contain up to 10%. The same applies to MgO, ZrO 2 and CaO.
  • the thickness of the untempered glass plate is the same as the thickness of the chemically strengthened glass plate 3.
  • the unstrengthened glass plate may be a smooth glass plate formed by a float method or the like, or a template glass plate having irregularities on the surface. Moreover, not only a flat glass plate but the glass plate which has a curved surface shape may be sufficient. A commercially available thing may be used for an unstrengthened glass plate, and what was manufactured by the well-known manufacturing method may be used.
  • the unstrengthened glass plate is prepared by, for example, preparing various amounts of various raw materials constituting the glass, heating and melting, and then homogenizing by defoaming or stirring, a well-known float method, down draw method (for example, fusion method), Or it can manufacture by shape
  • a glass ribbon may be used on-line during glass forming by a float method or a downdraw method (for example, a fusion method).
  • the functional film 5 is formed by applying the coating liquid on an unstrengthened glass plate and drying it. Drying may be performed by heating, or may be performed without heating (natural drying, air drying, etc.).
  • the functional film forming step is performed at a temperature of 450 ° C. or lower.
  • the temperature which performs a functional film formation process 400 degrees C or less is more preferable.
  • the unstrengthened glass plate can be sufficiently chemically strengthened through the functional film 5.
  • the minimum of the temperature which performs a functional film formation process will not be specifically limited if it is the temperature which can apply
  • Performing the functional film forming step at a temperature of 450 ° C. or less means that the coating solution (coating film) is applied between the time when the coating solution is applied on the unstrengthened glass plate and the time when chemical strengthening is performed in the next chemical strengthening step.
  • the temperature of the atmosphere in which the coating solution is applied, the temperature of the unstrengthened glass plate to which the coating solution is applied, the temperature of the coating film after application and drying, the drying temperature, and the chemical strengthening after drying The temperature and the like of the functional film 5 until the process is all 450 ° C. or lower.
  • the temperature of a coating film and the drying temperature of a coating film shall mean the temperature of the unstrengthened glass plate in which the coating film was formed, respectively.
  • the temperature of the functional film 5 shall mean the temperature of the non-tempered glass plate in which the functional film 5 was formed.
  • the temperature of the unstrengthened glass plate can be measured with a thermocouple, a radiation thermometer, or the like. For example, it can measure by attaching a thermocouple to the chemically tempered glass surface.
  • Application method As a coating method of the coating liquid, known wet coating methods (spin coating method, spray coating method, dip coating method, die coating method, curtain coating method, screen coating method, ink jet method, flow coating method, gravure coating method, bar coating method) Method, flexo coat method, slit coat method, roll coat method, etc.).
  • a spray method is preferable as a coating method of the coating solution from the viewpoint that sufficient unevenness can be easily formed.
  • the nozzle used in the spray method include a two-fluid nozzle and a one-fluid nozzle.
  • the particle size of the coating liquid droplets ejected from the nozzle is usually 0.1 to 100 ⁇ m, preferably 1 to 50 ⁇ m. If the particle size of the droplets is 1 ⁇ m or more, it is possible to form irregularities that sufficiently exhibit the antiglare effect in a short time. If the particle size of the droplet is 50 ⁇ m or less, it is easy to form moderate unevenness that sufficiently exhibits the antiglare effect.
  • the particle size of the droplet is the Sauter average particle size measured by a laser measuring device.
  • the particle size of the droplets can be adjusted as appropriate according to the type of nozzle, spray pressure, liquid volume, and the like. For example, in a two-fluid nozzle, the higher the spray pressure, the smaller the droplet, and the larger the liquid volume, the larger the droplet.
  • the arithmetic average roughness Ra and 60 ° specular gloss of the surface of the functional film 5 to be formed can be adjusted by the coating time, that is, the number of coated surfaces by spraying (number of overcoating).
  • An electrostatic coating method may be used as an application method of the application liquid when an antiglare film is formed as the functional film 5.
  • an application method by the electrostatic coating method for example, there is a method of charging and spraying the coating liquid using an electrostatic coating gun having a rotary atomizing head.
  • the coating liquid can be applied to a wide unstrengthened glass plate, the transport speed of the unstrengthened glass plate can be made relatively fast, and the required coating liquid
  • the roll coating method is preferable, the functional film 5 having a uniform film thickness can be formed, and the functional film 5 having an arbitrary film thickness that can be optically designed can be easily formed (that is, the film thickness).
  • the reverse roll coating method is more preferable.
  • a die coating method and an ink jet method are preferable.
  • the temperature of the atmosphere when applying the coating solution is preferably room temperature to 50 ° C., more preferably room temperature to 40 ° C.
  • the temperature of the unstrengthened glass plate when applying the coating solution may be the same as or different from the temperature of the atmosphere.
  • a heat insulating plate set in advance at a temperature equal to or higher than the temperature of the unstrengthened glass plate may be disposed under the unstrengthened glass plate to suppress the temperature drop of the unstrengthened glass plate.
  • a plurality of coating liquids having different compositions may be sequentially applied onto the unstrengthened glass plate.
  • a multilayer film can be formed as the functional film 5.
  • a coating solution containing no particles may be applied, and then a coating solution containing particles may be applied.
  • grains may apply
  • the next coating solution may be applied as it is on the formed coating film.
  • the coating film may be dried before coating. The drying at this time may be performed so that the liquid medium in the coating film is completely removed, or may be performed so that the liquid medium remains in the coating film.
  • Drying method As described above, drying when applying the coating liquid on the glass plate surface to form the functional film may be performed by heating or may be performed without heating. The heating may be performed simultaneously with the application by heating the unreinforced glass plate when applying the coating solution to the unreinforced glass plate, and the coating film is heated after the coating solution is applied to the unreinforced glass plate. You may go by.
  • the preferable upper limit of the drying temperature is the same as the preferable upper limit of the temperature at which the functional film forming step is performed. That is, the upper limit temperature is 450 ° C.
  • the lower limit of the drying temperature is not particularly limited. Since the polymerization of the silane precursor proceeds to some extent even in the case of natural drying, it is theoretically possible to set the drying temperature to a temperature around room temperature if there is no restriction on time.
  • the drying temperature is preferably 25 ° C. or higher, more preferably 30 ° C. or higher, from the viewpoint that sufficient drying conditions can be secured. From the viewpoint of chemical strengthening efficiency, the drying temperature is preferably 25 to 400 ° C, particularly preferably 30 to 400 ° C.
  • the drying time varies depending on the drying temperature, but is typically about 0.5 to 30 minutes, and preferably 1 to 5 minutes.
  • the unstrengthened glass plate on which the functional film 5 is formed in the functional film forming step is chemically strengthened. Thereby, the unstrengthened glass plate becomes the chemically strengthened glass plate 3, and the chemically strengthened glass plate 1 with a functional film is obtained.
  • Chemical strengthening can be performed by a known method.
  • a method of immersing the unstrengthened glass plate on which the functional film 5 is formed in a heated potassium nitrate (KNO 3 ) molten salt In this method, Na ions on the surface layer of the unstrengthened glass plate and K ions in the molten salt are exchanged to generate surface compressive stress and form a compressive stress layer.
  • KNO 3 molten salt in addition to KNO 3, for example, NaNO 3 may be one which contained about 5%.
  • the chemical strengthening is preferably performed so that a compressive stress layer having a desired surface compressive stress is formed on the unstrengthened glass plate.
  • the preferable ranges of the surface compressive stress and the thickness of the compressive stress layer are as described above.
  • the chemical strengthening treatment conditions for forming a compressive stress layer having a desired surface compressive stress on the unstrengthened glass plate vary depending on the glass composition of the unstrengthened glass plate, the thickness of the unstrengthened glass plate, etc., but the glass strain point temperature. It is typically immersed in the following 350 to 550 ° C. KNO 3 molten salt for 2 to 20 hours. From an economical point of view, the chemical strengthening treatment conditions are preferably immersed in KNO 3 molten salt at 350 to 500 ° C. for 2 to 16 hours, and immersed in KNO 3 molten salt at 350 to 500 ° C. for 2 to 10 hours. More preferred.
  • the chemically strengthened glass plate 1 with the functional film including the chemically strengthened glass plate 3 and the functional film 5 is obtained.
  • a predetermined amount of hollow silica particles are obtained as in Patent Document 1 by performing the functional film forming step at a temperature of 450 ° C. or lower. Even if it does not contain, the unstrengthened glass plate can be sufficiently chemically strengthened through the functional film 5 in the subsequent chemical strengthening step.
  • a compressive stress layer having a compressive stress of 500 MPa or more can be formed in a thickness of 20 ⁇ m or more on the surface layer of the surface of the unreinforced glass plate in contact with the functional film 5.
  • the functional matrix formation step is performed at a temperature of 450 ° C. or lower, so that the silica matrix constituting the functional membrane 5 can pass ions, and the ion exchange through the functional membrane 5 is performed in the chemical strengthening step. This is considered to be done well.
  • the reason why it is necessary to include the hollow silica sol at a certain ratio or more in the above-mentioned Patent Document 1 is that the matrix is dense because the low-reflection film is baked at a high temperature, and ions are contained therein. It is thought that it cannot pass.
  • a chemically strengthened glass plate with a functional film can be obtained by performing chemical strengthening after the film is formed.
  • the manufacturing method of the chemically strengthened glass plate with a functional film of this invention is a functional film at the temperature of 450 degrees C or less from the said coating liquid.
  • a glass plate that is not heat-treated at a temperature higher than 450 ° C. is used as a starting material, and the method may include a step of chemically strengthening the glass plate.
  • the chemically strengthened glass plate with a functional film obtained by the method for producing a chemically strengthened glass plate with a functional film of the present invention can be used for various applications depending on the type of the functional film.
  • Specific examples include transparent parts for vehicles (headlight covers, side mirrors, front transparent substrates, side transparent substrates, rear transparent substrates, instrument panel surfaces, etc.), meters, architectural windows, show windows, displays (notebook type) PC, monitor, LCD, PDP IV, ELD, CRT, PDA, etc.), LCD color filter, touch panel substrate, pickup lens, optical lens, eyeglass lens, camera component, video component, CCD cover substrate, optical fiber end surface, projector component , Copier parts, transparent substrates for solar cells (cover glass, etc.), mobile phone windows, backlight unit parts (light guide plates, cold cathode tubes, etc.), LCD brightness enhancement films, organic EL light-emitting element parts, inorganic EL light emission Element parts, phosphor light emitting element parts, optical filters, end faces of optical parts, lighting A lamp, a
  • the article of the present invention includes the above-described chemically strengthened glass plate with a functional film or the chemically strengthened glass plate with a functional film obtained by the above-described manufacturing method.
  • the article of the present invention may be composed of the chemically strengthened glass plate with the functional film, or may further include other members other than the chemically strengthened glass plate with the functional film. Further, a functional film may be provided on a part of the chemically strengthened glass plate.
  • Examples of the article of the present invention include those mentioned above as the uses of the chemically strengthened glass plate with a functional film, devices provided with any one or more of them. Examples of the device include a solar cell module, a display device, and a lighting device as an example in which the functional film is an antiglare film (may or may not have low reflectivity) or a low reflection film. Is mentioned.
  • the solar cell module includes a solar cell and a transparent substrate (cover glass or the like) disposed on each of the front and back surfaces of the solar cell in order to protect the solar cell, and at least one of the transparent substrates (preferably a transparent substrate) Are preferably those using the above-mentioned chemically strengthened glass plate with a functional film as a transparent substrate on the front side.
  • the display device include a mobile phone, a smartphone, a tablet, and a car navigation.
  • the illumination device include an organic EL (electroluminescence) illumination device and an LED (light emitting diode) illumination device.
  • Example 3 to 11 and Examples 14 and 15 are examples, and Examples 1, 2, 12, 13, and 16 are comparative examples.
  • the measurement / evaluation method and materials (source or preparation method) used in each example are shown below.
  • glossiness As the glossiness of the surface of the antiglare film, 60 ° specular glossiness was measured. The 60 ° specular gloss was measured at a substantially central portion of the antiglare film by using a gloss meter (PG-3D type, manufactured by Nippon Denshoku Industries Co., Ltd.) according to the method defined in JIS Z8741: 1997.
  • the glossiness of the surface of the antiglare film is influenced by the reflection of the back surface of the glass plate by attaching black vinyl tape to the back surface (surface opposite to the antiglare film) of the chemically strengthened glass plate with antiglare film. It measured in the state which lost. It shows that it is excellent in anti-glare property, so that glossiness is small.
  • the arithmetic average roughness Ra of the surface of the antiglare film was measured by a method described in JIS B0601: 2001 using a surface roughness meter (manufactured by Tokyo Seimitsu Co., Ltd., Surfcom (registered trademark) 1500DX).
  • the reference length lr (cut-off value ⁇ c) for the roughness curve was 0.08 mm.
  • Td Transmissivity difference
  • T1-T2 T1-T2 (1)
  • T1 is the average transmittance (%) of the chemically strengthened glass plate with a low reflection film
  • T2 is the average transmittance (%) of the glass plate before forming the low reflection film.
  • the film thickness d (nm) of the low-reflection film is a spectrophotometer (Otsuka Electronics Co., Ltd.) with a black vinyl tape attached to the back surface (surface opposite to the low-reflection film) of the chemically tempered glass plate with the low-reflection film.
  • the reflectance of the low-reflection film is measured in the wavelength range of 300 to 780 nm using an instantaneous multi-metering system MCPD-3000), and the lowest reflectance (bottom reflectance R min ) obtained and the low-reflection film
  • the refractive index n is calculated by the following formula (2) from the refractive index n s of the glass plate before forming, and the following formula is calculated from the obtained refractive index n and the wavelength ⁇ (nm) at the bottom reflectance R min . Calculated according to (3).
  • R min (n ⁇ n s ) 2 / (n + n s ) 2 (2)
  • n ⁇ d ⁇ / 4
  • the abrasion resistance of the surface of the anti-glare film was determined by attaching an eraser (Lion Secretariat, GAZA1K, length 18 mm ⁇ width 11 mm) to a rubbing tester (Ohira Rika Kogyo Co., Ltd.) and attaching the eraser to 9.8 ⁇ 10 ⁇ 2. Horizontal reciprocation was performed on the surface of the antiglare film at a pressure of MPa. The difference (absolute value) in 60 ° specular gloss on the surface of the antiglare film before and after reciprocating the eraser 200 times was determined as wear resistance ⁇ G. The smaller the difference in 60 ° specular gloss, the better the wear resistance. The 60 ° specular gloss was measured on an article with an antiglare film in which a black tape was not attached to the surface opposite to the side on which the antiglare film was formed.
  • SiO 2 equivalent solid content concentration 29% by mass
  • SiO 2 equivalent solid content concentration 29% by mass
  • silica precursor solution (a-2) preparation of silica precursor solution (a-2)
  • a mixed solution of 7.9 g of ion exchange water and 0.2 g of 61% by mass nitric acid was added and stirred for 5 minutes.
  • 11.6 g of 1,6-bis (trimethoxysilyl) hexane manufactured by Shin-Etsu Silicone Co., Ltd., trade name “KBM3066”, solid content concentration of SiO 2 : 37 mass%) was added, and the mixture was added at 15 ° C. in a water bath at 60 ° C.
  • a silica precursor solution (a-2) having a solid content concentration in terms of SiO 2 of 4.3% by mass.
  • the solid content concentration in terms of SiO 2 is the solid content concentration when all Si of 1,6-bis (trimethoxysilyl) hexane is converted to SiO 2 .
  • Solid silica particle dispersion (b) A chain SiO 2 fine particle dispersion (trade name: “Snowtex OUP”, manufactured by Nissan Chemical Industries, Ltd., solid content concentration of 15.5% by mass of SiO 2 , average primary particle size of 10 to 20 nm, average aggregated particle size of 40 to 100 nm ).
  • the content of the coating solution (B) chain in solid silica particles in is 70 mass% with respect to SiO 2 in terms the solid content of the coating solution (B).
  • the average aggregate particle diameter of the chain solid silica particles in the coating liquid (B) was 70 nm.
  • Example 1 As a glass plate, a soda-lime glass plate (manufactured by Asahi Glass Co., Ltd., product name: FL1.1, size: 100 mm ⁇ 100 mm, thickness 1.1 mm, glass strain point temperature: 511 ° C.) was prepared. The glass plate was subjected to ultrasonic cleaning treatment in pure water, air-dried, treated in a preheating furnace at 420 ° C. for 120 minutes, and then immersed in a KNO 3 melting bath at 420 ° C. for 150 minutes. After the treatment, the glass plate was taken out and cooled at room temperature for 60 minutes, and a chemically strengthened glass plate was obtained by ultrasonic cleaning treatment and air drying in pure water. Table 1 shows the surface compressive stress of the obtained chemically strengthened glass plate and the thickness of the compressive stress layer.
  • Example 2 Except for changing the glass plate to an aluminosilicate glass plate (manufactured by Asahi Glass Co., Ltd., product name: glass before strengthening of Leoflex. Size: 100 mm ⁇ 100 mm, thickness 0.85 mm, glass strain point temperature: 556 ° C.) In the same manner as in Example 1, a chemically strengthened glass plate was obtained. Table 2 shows the surface compressive stress of the obtained tempered glass sheet and the thickness of the compressive stress layer.
  • aluminosilicate glass plate manufactured by Asahi Glass Co., Ltd., product name: glass before strengthening of Leoflex. Size: 100 mm ⁇ 100 mm, thickness 0.85 mm, glass strain point temperature: 556 ° C.
  • Example 3 Glass plate and its cleaning
  • a soda-lime glass plate manufactured by Asahi Glass Co., Ltd., product name: FL1.1, size: 100 mm ⁇ 100 mm, thickness 1.1 mm, glass strain point temperature: 511 ° C.
  • the surface of the glass plate was washed with sodium hydrogen carbonate water, rinsed with ion-exchanged water, and dried.
  • a chemically strengthened glass plate with an antiglare film was obtained by performing a chemical strengthening treatment in the same manner as in Example 1 except that the glass plate with an antiglare film was used instead of the glass plate of Example 1.
  • Table 1 shows the surface compressive stress, the thickness of the compressive stress layer, the glossiness, and the arithmetic average roughness Ra of the obtained chemically strengthened glass plate with an antiglare film.
  • Example 4 to 6 A chemically strengthened glass plate with an antiglare film in the same manner as in Example 3 except that the coating solution (A) was applied so as to have the arithmetic average roughness Ra shown in Table 1 under the coating conditions and drying conditions shown in Table 1.
  • Table 1 shows the surface compressive stress, the thickness of the compressive stress layer, the glossiness, and the arithmetic average roughness Ra of the obtained chemically strengthened glass plate with an antiglare film.
  • Example 7 The glass plate was changed to an aluminosilicate glass plate (manufactured by Asahi Glass Co., Ltd., product name: glass before strengthening of Leoflex. Size: 100 mm ⁇ 100 mm, thickness 0.85 mm, glass strain point temperature: 556 ° C.) A) was changed to the coating solution shown in Table 2, and the coating solution and drying conditions shown in Table 2 were applied in the same manner as in Example 3 except that the coating was applied so that the arithmetic average roughness Ra shown in Table 2 was obtained. A chemically strengthened glass plate with a glare film was obtained. Table 2 shows the surface compressive stress, thickness of the compressive stress layer, glossiness, and arithmetic average roughness Ra of the obtained chemically strengthened glass plate with an antiglare film.
  • Table 2 shows the surface compressive stress, thickness of the compressive stress layer, glossiness, and arithmetic average roughness Ra of the obtained chemically strengthened glass plate with an antiglare film.
  • Example 8 to 9 A chemically strengthened glass plate with an antiglare film was applied in the same manner as in Example 7 except that the coating solution was applied so as to have the arithmetic average roughness Ra shown in Table 2 under the coating solution, coating conditions, and drying conditions shown in Table 2. Obtained.
  • Table 2 shows the surface compressive stress, thickness of the compressive stress layer, glossiness, and arithmetic average roughness Ra of the obtained chemically strengthened glass plate with an antiglare film.
  • Example 10 to 11 A chemically strengthened glass plate with an antiglare film was obtained in the same manner as in Example 3 except that the coating liquid was applied so as to have the arithmetic average roughness Ra shown in Table 1 at the coating liquid and drying temperature shown in Table 1.
  • Table 1 shows the surface compressive stress, the thickness of the compressive stress layer, the glossiness, and the arithmetic average roughness Ra of the obtained chemically strengthened glass plate with an antiglare film.
  • Example 12 (Chemically strengthened glass plate and its cleaning)
  • a chemically strengthened aluminosilicate glass plate manufactured by Asahi Glass Co., Ltd., product name: Leoflex, size: 100 mm ⁇ 100 mm, thickness 0.85 mm, glass strain point temperature: 556 ° C.
  • the surface of the glass plate was washed with sodium hydrogen carbonate water, rinsed with ion-exchanged water, and dried.
  • Example 13 A chemically strengthened glass plate with an antiglare film was applied in the same manner as in Example 12 except that the coating liquid was applied so as to have the arithmetic average roughness Ra shown in Table 3 under the coating liquid, coating conditions, and drying conditions shown in Table 3. Obtained.
  • Table 3 shows the surface compressive stress, the thickness of the compressive stress layer, the glossiness, the arithmetic average roughness Ra, and the wear resistance ⁇ G of the obtained chemically strengthened glass plate with an antiglare film.
  • Example 14 (Production of glass plate with low reflection film)
  • an aluminosilicate glass plate manufactured by Asahi Glass Co., Ltd., product name: glass before strengthening of Leoflex. Size: 100 mm ⁇ 100 mm, thickness 0.85 mm, glass strain point temperature: 556 ° C.
  • the glass plate was preheated in a preheating furnace (manufactured by ISUZU, VTR-115). Coating the reverse roll coater (manufactured by Sanwa Seiki Co., Ltd.) on the glass plate with the coating solution (C) under the following conditions with the glass surface temperature kept at 30 ° C.
  • the coating liquid (C) was applied with a predetermined film thickness using a roll to produce a glass plate with a low reflection film.
  • the other conditions at the time of application are as shown in Table 2.
  • ⁇ Conveying speed of glass plate 8.5 m / min
  • ⁇ Gap between coating roll and conveyor belt 2.9 mm
  • ⁇ Indentation thickness between coating roll and doctor roll 0.6 mm.
  • As the coating roll a rubber lining roll lined with rubber (ethylene propylene diene rubber) having a surface hardness (JIS-A) of 30 was used.
  • As the doctor roll a metal roll having lattice-like grooves formed on the surface thereof was used. Then, it dried at 200 degreeC for 30 minutes, and obtained the glass plate with a low reflection film.
  • Example 2 shows the surface compressive stress, the thickness of the compressive stress layer, the transmittance difference Td, and the film thickness of the low reflective film of the obtained chemically strengthened glass plate with the low reflective film.
  • Example 15 to 16 A chemically strengthened glass plate with a low reflection film was obtained in the same manner as in Example 14 except that the drying temperature was changed to the temperature shown in Table 2.
  • Table 2 shows the surface compressive stress, the thickness of the compressive stress layer, the transmittance difference Td, and the film thickness of the low reflective film of the obtained chemically strengthened glass plate with the low reflective film.
  • Example 1 When Example 1 is compared with Examples 3 to 6 and 10 to 11, the chemically strengthened glass plates with antiglare films of Examples 3 to 6 and 10 to 11 are chemically strengthened after the formation of the functional film (antiglare film).
  • the thickness of the compressive stress layer of the chemically strengthened glass plate was equal to or greater than that of the chemically strengthened glass plate of Example 1 in which chemical strengthening was performed without forming a functional film.
  • the surface compressive stress of the chemically strengthened glass plate was equal to or higher than that of the chemically strengthened glass plate of Example 1.
  • Example 2 When Example 2 is compared with 7 to 9 and 14 to 16, the chemically strengthened glass plate with antiglare film of Examples 7 to 9 and the chemically strengthened glass plate with low reflection film of Examples 14 and 15 are functional films (antiglare).
  • Example 2 in which chemical strengthening was performed after formation of the film, low-reflection film, and the surface compressive stress of the chemically strengthened glass plate and the thickness of the compressive stress layer were chemically strengthened without forming a functional film. It was equal to or better than the chemically strengthened glass plate.
  • the chemically tempered glass plate with a low reflection film of Example 16 in which the coating film was dried at 500 ° C. had the surface compressive stress of the chemically tempered glass plate and the thickness of the compressive stress layer of the chemically tempered glass plate of Example 2.
  • Example 8 that has been chemically strengthened after forming the functional film can only be chemically strengthened at least as much as Example 2. Rather, it had sufficient wear resistance.
  • the process of forming the functional film is not only performed at a temperature of 450 ° C. or lower, but also by performing chemical strengthening after the functional film is formed, for example, densification is performed while maintaining a structure through which ions can pass. Abrasion is considered to improve.
  • the chemical strengthening glass plate with a functional film by which physical deterioration by the contact of an object was suppressed by chemically strengthening can be provided.
  • a method for producing a chemically tempered glass plate with a functional film capable of satisfactorily chemically strengthening the glass plate after forming the functional film, a chemically tempered glass plate with a functional film obtained by the production method, and a chemically tempered glass plate with the functional film can be provided.
  • physical deterioration due to contact with an object was suppressed by chemical strengthening after coating of the functional film.

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  • Surface Treatment Of Glass (AREA)

Abstract

L'invention concerne : un procédé de production d'une plaque de verre trempée chimiquement dotée d'un film fonctionnel, qui est capable d'effectuer de manière fiable une trempe chimique d'une plaque de verre après la formation d'un film fonctionnel ; une plaque de verre trempée chimiquement dotée d'un film fonctionnel qui est obtenue par ledit procédé de production ; et un article qui est pourvu de ladite plaque de verre trempée chimiquement dotée d'un film fonctionnel. Une plaque de verre trempée chimiquement dotée d'un film fonctionnel, est une plaque de verre trempée chimiquement qui est pourvue d'un film fonctionnel sur au moins une surface, une partie ayant le film fonctionnel contenant une matrice de silice présentant une résistance à l'usure qui est exprimée comme la différence entre le brillant spéculaire à 60 ° avant un test de résistance à l'usure et le brillant spéculaire à 60 ° après le test de résistance à l'usure, ladite différence étant inférieure ou égale à 20. Un procédé de production d'une plaque de verre trempée chimiquement dotée d'un film fonctionnel (1) comprenant une plaque de verre trempée chimiquement (3) et un film fonctionnel (5), comprend : une étape au cours de laquelle un liquide de revêtement, qui contient un précurseur de silice et un milieu liquide de telle sorte que la teneur en précurseur de silice est supérieure ou égale à 15 % en masse par rapport à la teneur en solides en termes d'oxydes dans le liquide de revêtement et la teneur en particules de silice creuses est inférieure à 10 % en masse par rapport à la teneur en solides en termes d'oxydes dans le liquide de revêtement, est appliqué sur une plaque de verre et séché sur celle-ci, formant ainsi un film fonctionnel (5) ; et une étape au cours de laquelle la plaque de verre, qui a été pourvue du film fonctionnel (5), est soumise à une trempe chimique, ce qui permet d'obtenir une plaque de verre trempée chimiquement dotée d'un film fonctionnel (1). À cet égard, l'étape de formation du film fonctionnel (5) est réalisée à une température inférieure ou égale à 450 °C.
PCT/JP2015/066087 2014-06-06 2015-06-03 Plaque de verre trempée chimiquement dotée d'un film fonctionnel, son procédé de production et article WO2015186753A1 (fr)

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JP2014117988A JP2017132644A (ja) 2014-06-06 2014-06-06 機能膜付き化学強化ガラス板、その製造方法および物品
JP2014-117988 2014-06-06

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JP2017178634A (ja) * 2016-03-28 2017-10-05 フクビ化学工業株式会社 高反射防止強化ガラスの製造方法
WO2017179360A1 (fr) * 2016-04-12 2017-10-19 日本電気硝子株式会社 Procédé et dispositif de fabrication de verre trempé
WO2018199431A1 (fr) * 2017-04-24 2018-11-01 엘지전자 주식회사 Verre incurvé et son procédé de fabrication
KR20180119087A (ko) * 2017-04-24 2018-11-01 엘지전자 주식회사 곡면 글라스 및 그 제조방법
CN108831851A (zh) * 2018-06-26 2018-11-16 通威太阳能（成都）有限公司 一种提高太阳能电池el不良分类效率的分选方法
DE112018002226T5 (de) 2017-04-28 2020-01-23 AGC Inc. Glassubstrat mit aufgebrachtem film, gegenstand und verfahren zur herstellung eines glassubstrats mit aufgebrachtem film
WO2022014650A1 (fr) 2020-07-17 2022-01-20 Ａｇｃ株式会社 Substrat de verre doté d'un film de silice
CN117075261A (zh) * 2023-09-28 2023-11-17 中建材光芯科技有限公司 一种小倍率高强度光学纤维锥及其制备方法和应用
US11885998B2 (en) 2020-02-07 2024-01-30 Corning Incorporated Method of treating a glass surface and treated glass articles
JP7486726B2 (ja) 2020-07-17 2024-05-20 国立大学法人信州大学 シリカ膜付き基板

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KR102490522B1 (ko) * 2017-11-14 2023-01-19 삼성전자주식회사 커버 글래스 및 이를 포함하는 전자 장치, 및 커버 글래스 제조 방법
KR102230270B1 (ko) * 2018-04-23 2021-03-22 한국항공대학교산학협력단 비침지 방식을 통한 유리의 이온교환 방법
WO2019209012A1 (fr) * 2018-04-23 2019-10-31 한국항공대학교산학협력단 Procédé d'échange d'ions du verre par technique de non-immersion

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WO2013099620A1 (fr) * 2011-12-26 2013-07-04 旭硝子株式会社 Procédé de réduction du gauchissement d'un substrat en verre provoqué par un traitement de trempe chimique, et procédé de production d'un substrat en verre par trempe chimique

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JP2002234754A (ja) * 2001-02-02 2002-08-23 Nippon Sheet Glass Co Ltd 強化された機能性膜被覆ガラス物品の製造方法
JP2006083045A (ja) * 2004-09-17 2006-03-30 Hitachi Ltd ガラス部材
US20110293928A1 (en) * 2010-05-28 2011-12-01 Wintek Corporation Method for Strengthening Glass and Glass Using the Same
WO2013099620A1 (fr) * 2011-12-26 2013-07-04 旭硝子株式会社 Procédé de réduction du gauchissement d'un substrat en verre provoqué par un traitement de trempe chimique, et procédé de production d'un substrat en verre par trempe chimique

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017178634A (ja) * 2016-03-28 2017-10-05 フクビ化学工業株式会社 高反射防止強化ガラスの製造方法
CN108463443B (zh) * 2016-04-12 2021-07-13 日本电气硝子株式会社 强化玻璃的制造方法及强化玻璃制造装置
WO2017179360A1 (fr) * 2016-04-12 2017-10-19 日本電気硝子株式会社 Procédé et dispositif de fabrication de verre trempé
CN108463443A (zh) * 2016-04-12 2018-08-28 日本电气硝子株式会社 强化玻璃的制造方法及强化玻璃制造装置
WO2018199431A1 (fr) * 2017-04-24 2018-11-01 엘지전자 주식회사 Verre incurvé et son procédé de fabrication
KR20180119087A (ko) * 2017-04-24 2018-11-01 엘지전자 주식회사 곡면 글라스 및 그 제조방법
US11584674B2 (en) 2017-04-24 2023-02-21 Lg Electronics Inc. Curved glass manufacturing method
KR102048993B1 (ko) * 2017-04-24 2019-11-27 엘지전자 주식회사 곡면 글라스 및 그 제조방법
DE112018002226T5 (de) 2017-04-28 2020-01-23 AGC Inc. Glassubstrat mit aufgebrachtem film, gegenstand und verfahren zur herstellung eines glassubstrats mit aufgebrachtem film
CN108831851B (zh) * 2018-06-26 2021-03-09 通威太阳能（成都）有限公司 一种提高太阳能电池el不良分类效率的分选方法
CN108831851A (zh) * 2018-06-26 2018-11-16 通威太阳能（成都）有限公司 一种提高太阳能电池el不良分类效率的分选方法
US11885998B2 (en) 2020-02-07 2024-01-30 Corning Incorporated Method of treating a glass surface and treated glass articles
WO2022014650A1 (fr) 2020-07-17 2022-01-20 Ａｇｃ株式会社 Substrat de verre doté d'un film de silice
JP7486726B2 (ja) 2020-07-17 2024-05-20 国立大学法人信州大学 シリカ膜付き基板
CN117075261A (zh) * 2023-09-28 2023-11-17 中建材光芯科技有限公司 一种小倍率高强度光学纤维锥及其制备方法和应用
CN117075261B (zh) * 2023-09-28 2024-04-05 中建材光芯科技有限公司 一种小倍率高强度光学纤维锥及其制备方法和应用

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